Be(OH ) 2 2 NaOH

AlF3 3NaF
SiF4 2 HF

Na2 [ Be(OH ) 4 ]

Na3 [ AlF6 ]
H 2 SiF6

KCN .Fe(CN ) 2 .Fe(CN )3 XanhBeclin Diesbach XVIII

CoCl3 .5 NH 3 amoniacat puapureo RED XIX
CoCl3 .5 NH 3 .H 2O amoniacat rozeo PINK XIX

Chromate and Dichromate Ions

+4

+3
+2

+5
In acid

In base

Cr(OH)3 lng tnh

THUYT MCH

W. Blomstrand & Jorgensen

1884

CoCl3 .6 NH 3

CoCl3 .5 NH 3

CoCl3 .4 NH 3

NH 3 Cl
Co

NH 3 NH 3 NH 3 NH 3 Cl
NH 3 Cl

Cl
Co

NH 3

NH 3 NH 3 NH 3 Cl

NH 3 Cl
Cl
Co

NH 3 NH 3 NH 3 NH 3 Cl
Cl

THUYT PHI TR-1892

1.C

A. Werner, 1866-1919
Noben
ha
hc nm
th c Ha
tr chnh
v Ha1913
tr ph

trong

nguyn t.
Ha tr chnh tng ng vi khi nim s oxi ha.
Ha tr ph tng ng khi nim s phi tr.

2.Nguyn t to phc c xu hng bo ha cc ha

tr chnh v ha tr ph. Ha tr chnh ch c
bo ha bng anion, cn ha tr ph c bo
ha bng anion v phn t trung ha.

CoCl3 .6 NH 3
Cl
NH 3
O
N
NH 3
Cl

CoCl3 .5 NH 3

NH 3
M
M N
Co
M O
M
NH 3

NH 3
Cl
NH 3

CoCl3 .4 NH 3

Cl
M

NH 3
O
Cl
N
NH 3

NH 3
N

Co
M O
M
NH 3

Cl
NH 3

Cl
M

NH 3

NH 3

Co
M O

NH 3

Cl
NH 3

Cl

CHNG 10. PHC CHT

Mt s nh ngha
1.
2.
3.
4.

Phc cht
S phi tr ca nhn trung tm
Dung lng phi tr ca phi t
ng phn phc cht: cis-trans, quang hc, phi tr, ion ha, lin kt

Hng s in ly v hng s bn ca ion phc

Thuyt lin kt ha tr - The Localized Electron Model
Thuyt trng tinh th - The Crystal Field Model
1. S tch cc orbital ha tr d ca nhn trung tm bi trng cc phi t
trong ion phc 8 mt u AL6x+
2. S phn phi cc e ha tr d trong ion phc 8 mt u
3. Nng lng lm bn bi trng tinh th Ws
4. Thuyt trng tinh th p dng cho ion phc bn mt u AL 4x+
5. Cc yu t nh hng n thng s tch
6. S to thnh cc ion phc c cu trc khc
7. u nhc im ca thuyt trng tinh th

Thuyt orbital phn t - The Molecular Orbital Model

KHI NIM
Coordination Chemistry
Hp cht phi
tr (phc cht)
l hp cht
ha hc m
phn t ca n
cha ion phc

Ion phc
L tp hp cc cation v anion
C

ion trung tm l kim loi

cc phi t

Trong ion phc-complex tn ti nguyn t trung tm

(nhn trung tm), thng l cc ion kim loi chuyn tip
v bao quanh n l cc nguyn t, phn t hay ion lin kt
gi l phi t-ligands
Ion phc c gi l cu ni-coordination sphere, l
vng cha nguyn t hoc ion trung tm v cc phi t.
S phi tr-coordination number l s lin kt ca
nhn trung tm vi cc phi t
Phc mang in tch c gi l ion phc- complex ion.
Cht m c cha mt hoc nhiu ion phc c gi l hp
cht phi tr-coordination compound .

[CoCl(NO2)
(NH3)4]+

What are the coordination number and the

oxidation number of the central atom in

[CoCl4(NH3)2]

[Cr(OH)4(H2O)2]

S
phi
tr
bin i ph
thuc vo bn
cht ca phi
t, nng ,
nhit , cu
ngoi.
Cu2+,
Ni2+, Zn2+ c
s
phi
tr
bin i. Co3+,
Cr3+, Rh3+, Ir3+,
Pt4+, Ir4+ c s
phi
tr
6

Dung lng phi tr ca

phi
t

Nhiu nguyn t v ion, nht l cc kim loi

chuyn tip, c nhiu orbital trng do c th
nhn cc cp in t.
Dung lng phi tr ca phi t l s lin kt
ca 1 phi t lin kt vi nhn trung tm.
Phi t c dung lng phi tr bng 1 gi l phi
t n cng-monodentate ligands, nh NH3,
OH-, Cl-, NO2-, CNPhi t c dung lng phi tr ln hn 1 gi l
phi t a cng-polydentate ligand, nh H2NCH2-CH2-NH2, C2O42-.
Phi t a cng lin kt vi nhn trung tm to
thnh vng 5 hoc vng 6 gi l phc cht vng
cng-chelate.

Chelates
Metals and Chelates in Living
Systems

Cch gi tn phc cht

1.

2.

3.

4.

5.

Trong tn phc cht, u tin l phi t, ri n nguyn

t/ion trung tm, tt c chng c vit lin nhau.
Khi vit tn phc cht t cng thc, tn cc phi t sp xp
theo th t bng ch ci m khng tnh n cc s u
ng. Khi vit cng thc t tn, cc phi t anion t trc
phi t trung ha v tun theo trt t bng ch ci.
S phi tr ca phi t t trc phi t. Nu tn ca phi
t bn thn n c ch s, th t du ngoc n cho tn
phi t v ch s phi tr ca phi t.
Tn ca cation phc l tn ca nguyn t trung tm. Tn
ca anion phc thng thm ui ate vo cui nguyn t
trung tm. Trong mt s trng hp, s oxi ha ca nguyn
t trung tm c vit bng ch s Lam trong ngoc
n.
Khi vit cng thc hay tn ca phc cht, phi t cc ion
theo th t cation ri n anion.

Vit tn ca:
[CrCl2(NH3)4]+
Tetraamminedichloro-crom(III) ion
K[PtBrCl2NH3].
Kalium Amminebromodichloro-platinum(II)
Vit cng thc ca:
triamminechlorodinitrito-O-platinum(IV) ion
[PtCl(ONO)2(NH3)3]+
sodium hexanitrito-N-cobaltate(III).
Na3[Co(NO2)6]

1.

2.

3.

HNG S IN LI V
HNG S BN CA ION
PHC
Trong nc, phn t phc cht

phn li thnh ion cu ngoi v ion

cu ni.
Sau ion phc in li yu tng
nc ra cc phi t.
i lng c trng cho s in li
ca ion phc gi l:
hng s bn tng cng-nb v

AgCl ( s ) 2 NH 3 (aq
)

Ag ( NH 3 )2

(aq ) Cl (aq )

 Ag ( NH 3 )2

AgCl ( s ) 2 NH 3 (aq
)

(aq ) Cl (aq )

T 1.81011

AgCl ( s ) Ag (aq ) Cl (aq )

1.610

Ag ( NH 3 ) 2 (aq )
Ag (aq ) 2 NH 3 (aq )
2b

Ag ( NH 3 ) 2

2b ( K1 K 2 )b
2

Ag NH 3

Ag ( NH 3 )

K1b
Ag NH 3

Ag ( NH 3 ) 2

K 2b

Ag ( NH 3 ) NH 3

 nb ( K1 K 2 ...K n )b
G RT ln n H T S
o

Phc bn khi n cng ln, Go cng

nh Ho cng b v So cng ln

A x .aq

h , Ax

nL.aq
o

h,L

A x (k )

nL(k )

H H
o

o
h , ALxn

o
o

aq

nH

o
E

ALn .aq
o
H h , ALx
x

n H E
x
Ax L

AL
n (k )

Ax L

o
h,L

aq

o
h , A x

S S S
o

Ni( H 2O)6

o
2

.aq 4CN .aq

S o 0

o
1

Ni (CN )4

.aq 6 H 2O

Phn ng lm gim in tch ca ion phc l tng S ca

Ni( NH 3 )6

3En

S o 0

3
NiEn

6 NH 3

Phn ng to vng phc t phi t n cng l tng S c

? C kt ta khng trong dung dch cha cc cht sau:

0.1 mol AgNO3 ha tan trong 1 lt nc cha NH3 1M.
Nu 0.01 mol NaCl c thm vo dung dch th c kt
ta AgCl khng ?

Gi s 2b rt ln:

Ag (aq ) 2 NH 3 (aq) Ag ( NH 3 ) 2 (aq )

Initial conc.

0.10 M

1.00 M

0M

Change

-0.10 M

-0.20 M

+0.10 M

Eqlbrm conc.

(~0) M

0.80 M

0.10 M

[Ag+] tuy rt nh nhng khng th bng 0,

s dng hng s bn tng cng - 2b ca
phc tnh [Ag+]:

Ag (aq ) 2 NH 3 (aq) Ag ( NH 3 ) 2 (aq )

Initial concs.

0M

0.80 M

0.10 M

Changes

+x M

+2x M

-x M

Eqlbrm conc.

xM

0.80 + 2x M

0.10 - x M

[Ag(NH3)2]+
0.10-x
0.10
.
7
=
1.6
10
=
~
2b =
[Ag+][NH3]2 x(0.80 + 2x)2
x(0.80)2
0.10
x = [Ag ] =
(1.6 .107)(0.80)2
+

= 9.8.10-9 M

So snh tch nng ion vi tch s tan T

xem c kt ta hay khng:
TTG = [Ag+][Cl-] = (9.8.10-9)(1.0.10-2) = 9.8.10-11
T = 1.8.10-10
TTG < T

AgCl khng to kt ta trong iu kin ny.

THUYT LIN KT HA
TR
Valence Bond Theory

THUYT LIN KT HA
TR
The Localized Electron
Model

Lin kt ca ion trung tm vi

cc phi t l lin kt cho
nhn

Ion trung tm c s lai ha

Cc AO trng ca ion trung

tm nhn cc cp e cha phn
chia ca cc phi t

Phi t l cht cho (donor),

nhn trung tm l cht nhn
(acceptor)

1927 thuyt axit-bazo ca Liuyt

N. Sidgwick, 1873-1952, UK, vn dng cho
phc cht

BF3 (k ) : NH 3 F3 B NH 3 (r )

NH 3
]
3

Co 6 : NH 3
Z
NH 3

NH 3

[
3
Co

^
NH 3

NH 3

NH 3

Cu 2 NH 3 [Cu ( NH 3 ) 2 ]
sp

4s 4 p

10

Cu (3d )

3d

NH 3 NH 3

Co 4Cl [CoCl4 ]
sp3

4s
2

Co (3d )

3d

4p

Cl

Cl Cl Cl

Pt

4Cl [ PtCl4 ]
dsp2

Pt (5d )

6s

5d

6p

Cl Cl Cl Cl

Co 6 NH 3 [Co( NH 3 )6 ]
d2sp3 s lai ha trong

Co (3d )

3d

NH 3

NH 3

4s

4p

NH 3 NH 3 NH 3 NH 3

3 [ Fe( H 2O )6 ]3

Co 6 F [CoF6 ]

[ FeF6 ]

[ Ni ( NH 3 )6 ]

sp3d2 s lai ha ngoi

Co3 (3d 6 )

3d

4s

4d

4p

TNH CHT T CA
PHC
Phc cht c e c thn l
thun t.
Phc cht khng c e c
thn l nghch t.
Moment t spin:

S n(n 2) B
n s e c thn

eh
9.274 1024 J / T
2me

U IM V HN CH
THUYT LIN KT HA
TR
u im:
- M t n gin v c th cc lin
kt trong phc cht
- Gii thch c t tnh ca phc
cht
Hn ch:
- Khng gii thch c mu sc
ca phc cht

THUYT TRNG TINH

TH
Crystal Field Theory

1.

2.

3.

THUYT TRNG TINH

TH
Crystal
Theory
Phc
cht tn Field
ti v bn
do tng

tc
tnh in gia nhn trung tm v cc
phi t
Phi t l in tch im khng c cu
trc
Nhn trung tm c cc AO-d ha tr
ng nng lng s b phn tch thnh
cc mc khc nhau do tc dng ca
trng to bi cc phi t

Xt trng phi t trong

phc bt din AL6x+
A

S tch cc orbital ha tr d ca
nhn trung tm bi trng cc
phi t
Cc orbital
mu vng
c
nng
lng cao
hn
cc
orbital mu
do tc
dng
ca
trng phi
t

eg - E2

-thng s tch
t2g E1

[cm-1]; 1 cm-1 = 11,9 J/mol

=E2 E1
3E1 + 2E2 = 0

E2 =
0.6

E1 = 0.4

Fig. 22.17

>
P<

P l nng lng cp i ca
electron
L nng lng cn thit chuyn 2 e c
thn vi spin cng du t 2 orbital cng
nng lng vo 1 orbital m chng

 < P: HS

> P: LS

Ligand-filed stabilization
energies (LFSE)

Nng lng bn ha bi trng tinh

th (LB) s gim nng lng ca cc e
in vo orbital d c nng lng thp so
vi nng lng trung bnh ca orbital trong
trng tinh th

s cng ln th phc cht cng bn.

s ch ng gp vo nng lng lin kt

ch khng phi l nng lng lin kt
trong ion phc.

 s (0.4n1 0.6n2 ) O

s - nng lng bn ha bi trng tinh th

n1 - s e trn cc orbital t2g (E1 bn di)
n2 - s e trn cc orbital eg

HiU NG JAHN-TELLER
1937

Trng thi e suy bin ca

1 phn t khng thng
hng l khng bn,
phn t s bin dng
hnh hc gim tnh
i xng v suy
bin

Highspin:
electrons
can occupy
both lowand highenergy
orbitals.

[Cr ( H 2O )]

0 11000cm
2

[ Mo( H 2O)6 ]

[W ( H 2O)6 ]
3

[Cr ( H 2O)]

0 25000cm

0 30000cm

0 20500cm

 for Tetrahedral Complexes vs Square

Planar
Tetrahedral = 4/9 Octahedral so
Tetrahedral Complexes are Usually High Spin
Square Planar Complexes are Always Low Spin

Fig. 22.23

t
s (0.6n1 0.4n2 ) t

Square Planar Crystal

Field

Fig. 22.24

Orbitals split differently,

depending on the geometry
of the ligand field.

TNH CHT T CA
PHC
Phc cht c e c thn l
thun t.
Phc cht khng c e c
thn l nghch t.
Moment t spin:

S n(n 2) B
n s e c thn

eh
9.274 1024 J / T
2me

Mu ca ion phc v
hp cht phi tr

Cc ion c cu hnh e sau s khng chuyn e trogn vng VIS:

A noble-gas electron configuration.
An outer shell with 18 electrons.
An 18 + 2 configuration (for example, Sn2+).

 (6.61 1034 Js) (3 10

8 m / s)
23

J
/
ion

(6.023
10

ion / mol ) 239kJ / mol

7
5 10 m

hC
h N A
N A[ J ]

S hp th nh sng v
nguyn nhn to mu
cn li nh
nh
sng
sc
sng xanh i

vng b hp
th

nh sng
xanh b hp
th

qua lm dung
dch c
nhn thy
mu xanh
cn li nh
sng vng i qua
lm dugn dch c
mu vng
blue: 400-490 nm
yellow-green: 490-580 nm
red: 580-700 nm

Qua
n h
gia
cht
hp
th
v
mu
qua
n
st

nh hng ca phi t
ln mu ca hp cht
phi tr

U IM V HN CH
THUYT TRNG TINH TH
u im:

- L m hnh n gin v d hiu

- Gii thch c nhiu tnh cht ph hp vi thc
nghim: tnh c mu, t tnh

Hn ch:

- Coi phi t l in tch im khng c cu trc:

phn t trung ha H2O, NH3 to trng mnh
hn anion OH-, Cl-, F-; H2O c cc mnh hn NH3
nhng to trng yu hn; CN- bn knh nh
hn F- nhng to trng mnh hn nhiu
- Khng gii thch c ph chuyn dch in
tch, khng cp n lin kt Pi trong phc vi
CO, anken, ankin, xiclopentadien

THUYT ORBITAL PHN

T
The
Molecular
Phn
t phc
cht l 1 htOrbital
thng nht gm
nguyn t trung tm v cc phi t
Model
Chuyn ng ca e trong phn t m t bng

hm sng MO
MO l t hp tuyn tnh cc AO ca nguyn t
trung tm v phi t
Cc AO t hp tuyn tnh khi c cng nng
lng, mt e v i xng
MO t hp c MO lin kt v MO phn lin kt
Qui tc in e vo MO ging nh AO

[ ML6 ]

x* *y z*
s*

x*2 y 2 z*2

z 2 c5 3d z 2 c6 (2 5 2 6 1 2 3 4 )
x2 y 2 c7 3d x2 y 2 c8 ( 1 2 3 4 )

xy xz yz

6
x2 y 2 z 2
x y z

x c3 4 px c4 ( 1 3 )
y c3 4 p y c4 ( 2 4 )
z c3 4 pz c4 ( 5 6 )

s c1 4 s c2 ( 1 2 3 4 5 6 )

[CoF6 ]3

o 156kJ / mol

2
s

6
p

4
d

4
d

*2
d

[Co( NH 3 )6 ]3

o 265kJ / mol
2 6 4 6
s p d d

[Ti ( H 2O )6 ]

z*2 x*2 y 2

d z 2 d x2 y 2

d
d xy d xz d yz

xy xz yz
z 2 x2 y 2

d 2 sp 3

H 2O H 2O

H 2O

H 2O H 2O H 2O

x y z